CN101910205B

CN101910205B - Multistage process for the polymerization of olefins

Info

Publication number: CN101910205B
Application number: CN2008801225908A
Authority: CN
Inventors: S·米汉; E·查西亚
Original assignee: Basell Polyolefine GmbH
Current assignee: Basell Polyolefine GmbH
Priority date: 2007-12-24
Filing date: 2008-12-23
Publication date: 2012-11-21
Anticipated expiration: 2028-12-23
Also published as: CN101910205A; EP2225283A1; US7999043B2; WO2009080359A1; US20110003948A1; EP2225283B1

Abstract

A multistage process for the homo or copolymerization of ethylene carried out in the presence of a catalyst system comprising at least one polymerization catalyst (A) based on a late transition metal component having a tridentate ligand which bears at least two ortho.ortho-disubstituted aryl radicals, at least one Ziegler polymerization catalyst (B), and at least a Lewis acid activating compound (C), wherein the molar ratio of the metal of the activating compound (C) to the late transition metal of catalyst (A) is different in the two polymerizations steps. Catalysts (A) and (B) may be selectively controlled by varying the amount of activating compound (C).

Description

The multi-stage process that is used for olefinic polymerization

Invention field

The present invention relates to a kind of multi-stage process that is used for olefinic polymerization, said method is carried out in the presence of polymerizing catalyst, at least a Ziegler polymerization catalyst and at least a activating compounds that at least a later transition metal component with tridentate ligand is the basis.

Background of invention

Multimodal type Vilaterm demonstrates the character of improvement with respect to the single peak type Vilaterm, and therefore people are widely used in various application with it in the art, for example in fiber, moulded work, film and the pipe.Multimodal polyethylene has the polymerization composition of a plurality of different molecular weights, so its molecular-weight-distribution has the molecular weight peaks more than; The MWD broad of multimodal polyethylene, therefore for unimodal Vilaterm, it also is easier to processing.

The known various methods that prepare multimodal polyethylene in this area comprise melting mixing behind the still, the single stage process of in the presence of the catalyst system of the mixture that comprises different catalysts, carrying out and multiple-stage method.Used method has determined poly character, because the character of multimodal polyethylene not only depends on the character of its single polymkeric substance composition, and depends on these composition blended character.Bad mixed nature itself can cause low stress splitting resistance, and the creep properties of the goods that this Vilaterm is processed has a negative impact.

The melting mixing technology is carried out in forcing machine usually, its costliness, heavy and consuming time; And the mixed nature of each composition is not enough for many application.

Alternatively, can use to comprise at least two kinds of differing ethylene polymerizing catalysts and can prepare catalyst of polyethylene system, in single reactor drum, prepare multimodal polyethylene with different molecular weight.

It all is known in the art that catalyzer is closed in each adoption, for example Z-type catalyst, metalloscene catalyst and the transition metal complex that comprises non-cyclopentadienyl ligands of research and development recently.For example, WO 98/27124 discloses 2 of iron and cobalt, and two (imino-) pyridine complexs of 6-are as the catalyzer of ethylene homo or copolymerization.J.Am.Chem.Soc.127, described among the 13019-13029 (2005) some two-imino-pyridine Z-type catalyst and the activity in vinyl polymerization thereof.

Described the catalyst mixture that comprises the different activities center in the prior art, had the polymkeric substance that broad distributes in order to preparation in the preparation method who uses single reactor drum.For example, described among the WO95/11264 and used the catalyst composition that comprises at least two kinds of different Ziegler-types or metallocene-type ethylene rolymerization catalyst, it discloses the Vilaterm that the combined preparation of using this catalyzer has wide molecular weight distribution.

Described a kind of catalyst composition that is used for alpha-olefine polymerizing among the WO 99/46302, it comprises 2, two (imino-) the pyridyl iron catalysts of 6-and another kind of catalyzer, for example zirconocene or Z-type catalyst; Disclose among the WO 05/103096 and comprised 2, the catalyst composition of two (imino-) pyridine iron catalyzer of 6-and hafnocene catalyzer.

Above-mentioned document description the application of hybrid catalyst system in single polymerization procedure.But, if in single reactor drum, make spent mixed catalyst carry out the successive polymerization of alkene, then there is a problem, be exactly the ratio that the character of resulting polymers significantly depends on the active site of existence.Therefore, the fluctuation of the composition of the mixed catalyst of different batches possibly cause having different ratios by the polymeric constituent that single catalyst component forms.And catalyst aging if especially a kind of other component of ratio of component is responsive more, then also possibly causes even when using the catalyzer of same batch, still obtains Different products.The fluctuation of polymerizing condition also possibly influence the activity of the catalyst component that uses by different way, thereby also possibly make the polymeric constituent that is formed by single catalyst have different ratios.Therefore be starved of, especially when making spent mixed catalyst, be used to control the method for the composition of formed polymkeric substance.

Multistage polymerization is carried out at least two steps usually, and it can or carry out in the reactor drum of two serial operations in same reactor drum at least; Each step is carried out under different process conditions, in order to obtain to have the Vilaterm composition of different molecular weight and/or different monomers composition.The most common way that obtains the composition of different molecular weight is in reactor drum, to use different hydrogen concentrations, and adopts different comonomer concentrations can obtain the different compositions of forming.

This multimodal polyethylene mixture uses the cascade form of reactor drum usually; The two or more polymerization reactor preparations that promptly are connected in series; Wherein being aggregated in first reactor drum of lower-molecular-weight component taken place; Being aggregated in the subsequent reactor of high molecular weight component carry out (referring to; M.

W.Nei β l " Bimodale Polymerwerkstoffe auf der Basis von PP und PE " in " Aufbereiten von Polymeren mit neuartigen Eigenschaften " 3-25 page or leaf for example; VDI-Verlag, D ü sseldorf 1995).

The unfavorable property of this method is to add more a large amount of hydrogen and has the composition of relatively low molecular weight with preparation, the result, and particularly the low molecular weight polyethylene composition has low-down contents of ethylene, is usually less than 0.3.And, when in different reactor drums, using different hydrogen concentrations, technically be difficult to also prevent that hydrogen or any other molecular weight regulator that in first reactor drum, adds from getting into second reactor drum.

When in each polymerization procedure, using different comonomers or different comonomer concentration, to face same problem; In this case, the angle from device then needs very high expense.

Attempted the whole bag of tricks in order to address this problem people.Thereby; Among WO 00/50466 and the WO02/24768 polymerization method that makes spent mixed catalyst has been described; In each method, two kinds of different mixed catalysts are introduced in the reactor drum, and are different but described two kinds of mixed catalysts comprise identical catalyst component ratio.Then, can control the polymeric constituent of formation and the ratio between the another kind of component through the ratio of regulating two kinds of mixed catalysts.But, in order to realize this purpose, must two different measuring systems be installed on a reactor drum and it is regulated each other, and for the polymer type of each preparation, must prepare and use two kinds of different catalyst solids.

Therefore, the purpose of this invention is to provide a kind of multi-stage process that can overcome the problems referred to above.

Summary of the invention

Find that surprisingly this purpose can realize that said multistage polymerization method carries out through the amount that changes activating compounds through multistage polymerization method in the presence of the special catalyst system.In fact, the applicant finds that unexpectedly the amount that changes activating compounds can optionally be controlled the activity of specific family ethylene rolymerization catalyst, thereby molecular weight and the comonomer that can control gained Vilaterm composition are formed.

Therefore; The objective of the invention is to be used for the multi-stage process of ethylene homo or copolymerization, it is included in catalyst system and exists down, at least two polymerization procedures to ethene and optional one or more more high alpha-olefin carry out polymerization; Said catalyst system comprises at least a polymerizing catalyst based on the rear transition metal component (A), it has and brings to few two ortho positions; The tridentate ligand of ortho position-disubstituted aryl, at least a Ziegler polymerization catalyst (B) and at least a lewis acid activation compound (C); Wherein in two polymerization procedures, the metal of said activating compounds (C) is different with the mol ratio of the rear transition metal of catalyzer (A).

The mol ratio of the rear transition metal of the metal of Z-type catalyst (B) and catalyzer (A) is preferably 500: 1-1: 100, more preferably 100: 1-1: 50, even more preferably 50: 1-1: 1.

According to embodiment preferred, method of the present invention comprises:

-the first polymerization procedure, wherein the mol ratio of the rear transition metal of metal in the activating compounds (C) and catalyzer (A) is 1,500: 1-1: 1, more preferably 1,000: 1-100: 1, even more preferably 900: 1-300: 1;

-the second polymerization procedure, wherein the mol ratio of the rear transition metal of metal in the activating compounds (C) and catalyzer (A) is 20,000: 1-1,500: 1, preferred 10,000: 1-2,000: 1, more preferably 9,000: 1-3,000: 1.

Usually; First polymerization procedure carries out in the presence of a small amount of activating compounds (C); Its activation catalyzer (A), in order to obtaining first ethylene homo or multipolymer composition, and second polymerization procedure carries out in the presence of higher amount activating compounds (C); This activating compounds (C) reduces the activity of late transition metal catalyst (A), and activation Z-type catalyst (B) is to obtain second ethylene homo or polymeric composition comprising body simultaneously.

Described two polymerization procedures can or carry out in the reactor drum of two serial operations in same reactor drum at least.

It is 0.900-0.970g/cm that method of the present invention can provide density ³, M _wBe 100,000-900,000g/mol, M _w/ M _nBe at least 12, preferably at least 15, the more preferably Vilaterm of 20-50.

According to preferred embodiment, method of the present invention provides multimodal polyethylene, and it comprises:

At least a Alathon of-5-95%wt. or ethene and up to the multipolymer of the more high alpha-olefin of 2%mol., its density is 0.950-0.975g/cm ³, M _wBe 10,000-100,000g/mol, M _w/ M _nBe included between the 3-15 and

At least a Alathon of-5-95%wt. or ethene and up to the multipolymer of the more high alpha-olefin of 15%mol, its density is 0.870-0.955g/cm ³, M _wBe 100,000-2,000,000g/mol, M _w/ M _nBe included between the 8-80.

Detailed Description Of The Invention

Unless otherwise indicated, otherwise " polymkeric substance " refer to homopolymer or comprise the multipolymer of two or more comonomers.

Unless otherwise indicated, otherwise " polymerization " refers to homopolymerization or copolymerization.

Unless otherwise indicated, otherwise " Vilaterm " refers to the multipolymer of Alathon or ethene and at least a other comonomer.

" multimodal polyethylene " refer to owing to there are two polymkeric substance compositions with different molecular weight at least, thereby have at least one bimodal molecular weight distribution curve, has at least two molecular weight peaks, perhaps on the maximum peak side, has the Vilaterm of at least one flex point.Multimodal polyethylene also possibly show three or more a plurality of molecular weight peaks (perhaps on a side of maximum peak, having at least two flex points), and this is because there are at least three polymkeric substance compositions with different molecular weight.

" Alathon " refer to comprise the multiple ethylene monomer unit and the amount of the different sorts comonomer that possibly exist limited, thereby the melt temperature T of polymkeric substance under any circumstance _mBe about 125 ℃ or higher polymkeric substance, wherein said melt temperature T _mFor following detailed description, in the temperature at melting peak peak place.T _mMode according to ISO 11357-3 is measured, i.e. heating for the first time is heated to 200 ℃ with the heating rate of 20 ℃/min, and to-10 ℃, heating for the second time is heated to 200 ℃ with the heating rate of 20 ℃/min with the rate of cooling dynamic crystallization of 20 ℃/min.Therefore, melt temperature T _m(peak of the melting peak of heating for the second time) is the temperature at the enthalpy-temperature curve peak place of the heating second time.

" ethylene copolymer " refers to comprise multiple ethylene monomer unit and at least one different types of other comonomer, and melt temperature is lower than T _m125 ℃ polymkeric substance.

Unless otherwise indicated, otherwise " molecular weight " refers to the weight-average molecular weight M according to following indication measurement _w

Unless otherwise indicated, otherwise the percentage number average of all one-components of mentioning among the application is based on weight, based on correspondent composition or comprise the gross weight of the mixture of those components.

Suitable late transition metal catalyst (A) is the complex compound of formula (I):

Wherein:

M is Fe or Co, preferred Fe,

E ^1CBe nitrogen or phosphorus, preferred nitrogen,

E ^2C-E ^4CBe carbon, nitrogen or phosphorus independently of one another, preferred carbon,

R ^1C-R ^3CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂-aryl, have 1-10 carbon atom on the alkyl and on aryl, having alkylaryl, halogen, the NR of 6-20 carbon atom ^18C ₂, OR ^18C, SiR ^19C ₃, organic group R wherein ^1C-R ^3CCan also be replaced by halogen, and/or two adjacent R ^1C-R ^3CCan also be connected to form 5-, 6-or 7-unit ring, and/or two adjacent R ^1C-R ^3CCan be connected to form and comprise at least one 5-that is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle,

R ^4C-R ^7CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂-aryl, have 1-10 carbon atom on the alkyl and on aryl, having alkylaryl, the NR of 6-20 carbon atom ^18C ₂, SiR ^19C ₃, organic group R wherein ^4C-R ^7CCan also be replaced by halogen, and/or two geminals or adjacent radicals R ^4C-R ^7CCan also be connected to form 5-, 6-or 7-unit ring, and/or two geminals or adjacent radicals R ^4C-R ^7CCan be connected to form and comprise at least one 5-that is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle, and when v is 0, R ^6CFor being connected to L ^1CKey, and/or R ^7CFor being connected to L ^2CKey, make L ^1CAnd have R ^4CCarbon atom form two keys, and/or L ^2CAnd have R ^5CCarbon atom form two keys,

U works as E ^2C-E ^4CIt is 0 during for nitrogen or phosphorus, works as E ^2C-E ^4CIt is 1 during for carbon,

L ^1C-L ^2CBe nitrogen or phosphorus, especially nitrogen independently of one another,

R ^8C-R ^11CBe C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂-aryl, have 1-10 carbon atom on the alkyl and on aryl, having the alkylaryl or the halogen of 6-20 carbon atom,

R ^12C-R ^17CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂-aryl, have 1-10 carbon atom on the alkyl and on aryl, having alkylaryl, halogen, the NR of 6-20 carbon atom ^18C ₂, OR ^18C, SiR ^19C ₃, organic group R wherein ^12C-R ^17CCan also be replaced by halogen, and/or two adjacent radicals R ^8C-R ^17CCan also be connected to form 5-, 6-or 7-unit ring, and/or two adjacent radicals R ^8C-R ^17CCan be connected to form and comprise at least one 5-that is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle,

V is 0 or 1 independently,

Radicals X ^CBe fluorine, chlorine, bromine, iodine, hydrogen, C independently of one another ₁-C ₁₀-alkyl, C ₂-C ₁₀-thiazolinyl, C ₆-C ₂₀-aryl, have 1-10 carbon atom on the alkyl and on aryl, having alkylaryl, the NR of 6-20 carbon atom ^18C ₂, OR ^18C, SR ^18C, SO ₃R ^18C, OC (O) R ^18C, CN, SCN, beta-diketon thing, CO, BF ₄ ^-, PF ₆ ^-Or the non-coordination anion of big volume, and radicals X ^COptional can being connected to each other,

Radicals R ^18CBe hydrogen, C independently of one another ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₆-C ₂₀-aryl, have 1-10 carbon atom on the alkyl and on aryl, having alkylaryl, the SiR of 6-20 carbon atom ^19C ₃, organic group R wherein ^18CCan also be replaced by halogen or nitrogen-containing group and oxy radical, and two radicals R ^18CCan also be connected to form 5-or 6-unit ring,

Radicals R ^19CBe hydrogen, C independently of one another ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₆-C ₂₀-aryl, have 1-10 carbon atom on the alkyl and on aryl, having the alkylaryl of 6-20 carbon atom, wherein organic group R ^19CCan also be replaced by halogen or nitrogen-containing group and oxy radical, and two radicals R ^19CCan also be connected to form 5-or 6-unit ring,

S is 1,2,3 or 4, preferred 2 or 3,

D for no lotus donor and

T is 0-4, preferred 0,1 or 2.

Three atom E in the molecule ^2C-E ^4CCan be identical or different.If E ^1CBe phosphorus, then E ^2C-E ^4CBe preferably carbon.If E ^1CBe nitrogen, then E ^2C-E ^4CBe preferably nitrogen or carbon, preferred carbon.

Substituent R ^1C-R ^3CAnd R ^12C-R ^17CCan in wide region, change.Possible organic substituent R ^1C-R ^3CAnd R ^12C-R ^17CBe for example following groups: straight or branched C ₁-C ₂₂-alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl; 5-to 7-unit naphthenic base, it can further have C ₁-C ₁₀-alkyl and/or C ₆-C ₁₀-aryl is as substituting group, for example Trimetylene, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane or cyclododecane; C ₂-C ₂₂-thiazolinyl; It can for straight chain, ring-type or side chain and two keys wherein can be in inside or end, for example vinyl, 1-allyl group, 2-allyl group, 3-allyl group, crotonyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base; C ₆-C ₂₂-aryl, it can further have alkyl as substituting group, for example phenyl, naphthyl, xenyl, anthryl, neighbour-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2; 5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3; 6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl; Perhaps arylalkyl, it can further have alkyl as substituting group, for example benzyl, neighbour-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein R ^1C-R ^3CIn two groups and/or two adjacent group R ^12C-R ^17CCan also choose wantonly and be connected to form 5-, 6-or 7-unit ring, and/or adjacent radicals R ^1C-R ^3CIn two and/or adjacent radicals R ^12C-R ^17CIn two can be connected to form and comprise the 5-that at least one is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle, and/or organic group R ^1C-R ^3CAnd/or R ^12C-R ^17CCan also be by halogen, for example fluorine, chlorine or bromine replace.In addition, radicals R ^1C-R ^3CAnd R ^12C-R ^17CCan be amino N R ^18C ₂Or N (SiR ^19C ₃) ₂,, alkoxyl group or aryloxy OR ^18C, for example dimethylamino, N-pyrrolidyl, pieolinyl, methoxyl group, oxyethyl group or isopropoxy, perhaps halogen, for example fluorine, chlorine or bromine.At organosilicon substituting group SiR ^19C ₃In, possible radicals R ^19CWith before to R ^1C-R ^3CMentioned carbon organic group is identical, wherein two radicals R ^19CCan also choose wantonly and be connected to form 5-or 6-unit ring, for example trimethyl silyl, triethylsilyl, butyl dimetylsilyl, tributyl silyl, tri-tert silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR ^19C ₃Group can also be bonded in E through oxygen or nitrogen ^2C-E ^4COn, for example trimethylsiloxy, silicoheptane alcoxyl base, butyl dimethylsilane oxygen base, tributyl siloxy-or tri-tert siloxy-.

Preferred radicals R ^1C-R ^3CBe hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, neighbour-dialkyl group-or substituted phenyl of adjacent-two chloro-, trialkyl-or the substituted phenyl of three chloro-, naphthyl, xenyl and anthryl.The organosilicon substituting group that is particularly useful is the trialkylsilkl that has 1-10 carbon atom on the alkyl, preferred trimethyl silyl.

Preferred radicals R ^12C, R ^14C, R ^15C, R ^17CBe hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine and bromine, preferred hydrogen.R ^12C, R ^14C, R ^15CAnd R ^17CBe preferably hydrogen.

Preferred radicals R ^13CAnd R ^16CBe hydrogen, methyl and chlorine.

Preferred radicals R ^8CAnd R ^10CBe halogen, especially chlorine.

Preferred radicals R ^9CAnd R ^11CBe methyl.

Preferred R ^12C, R ^14C, R ^15CAnd R ^17CIdentical and R ^13CAnd R ^16CIdentical.This situation also is preferred for above-mentioned preferred embodiment.

Substituent R ^4C-R ^7CAlso can in wide region, change.Possible organic substituent R ^4C-R ^7CBe for example following groups: C ₁-C ₂₂-alkyl, it can be straight or branched, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl; 5-to 7-unit naphthenic base, it can further have C ₁-C ₁₀-alkyl and/or C ₆-C ₁₀-aryl is as substituting group, for example Trimetylene, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane or cyclododecane; C ₂-C ₂₂-thiazolinyl; It can for straight chain, ring-type or side chain and two keys wherein can be in inside or end, for example vinyl, 1-allyl group, 2-allyl group, 3-allyl group, crotonyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base; C ₆-C ₂₂-aryl, it can further have alkyl as substituting group, for example phenyl, naphthyl, xenyl, anthryl, neighbour-,-, right-tolyl, 2,3-, 2,4-, 2; 5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3; 6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl; Perhaps arylalkyl, it can further have alkyl as substituting group, for example benzyl, neighbour-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein R ^4C-R ^7CIn two groups can also choose wantonly and be connected to form 5-, 6-or 7-unit ring, and/or R ^4C-R ^7CIn two geminal groups can be connected to form and comprise the 5-that at least one is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle, and/or organic group R ^4C-R ^7CCan also be by halogen, for example fluorine, chlorine or bromine replace.In addition, R ^4C-R ^7CCan be amino, NR ^18C ₂Or N (SiR ^19C ₃) ₂, for example dimethylamino, N-pyrrolidyl or pieolinyl.At organosilicon substituting group SiR ^19C ₃In, possible radicals R ^19CWith before to R ^1C-R ^3CMentioned carbon organic group is identical, wherein two radicals R ^19CCan also choose wantonly and be connected to form 5-or 6-unit ring, for example trimethyl silyl, triethylsilyl, butyl dimetylsilyl, tributyl silyl, tri-tert silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR ^19C ₃Group can also be connected on the carbon that has it through nitrogen.When v is 0, R ^6CFor being connected to the key of L1C, and/or R ^7CFor being connected to L ^2CKey, thereby L ^1CWith contain R ^4CCarbon atom form two keys, and/or L ^2CAnd have R ^5CCarbon atom form two keys.

Preferred radicals R ^4C-R ^7CBe hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, neighbour-dialkyl group-or substituted phenyl of adjacent-two chloro-, trialkyl-or the substituted phenyl of three chloro-, naphthyl, xenyl and anthryl.Amide substituents NR ^18C ₂Also be preferred; Especially secondary amide, for example dimethylformamide, N-ethylmethyl amide, diethylamide, N-methyl-propyl acid amides, N-isopropyl methyl acid amides, N-ethyl sec.-propyl acid amides, dipropyl acid amides, diisopropylamide, N-methylbutyl acid amides, N-ethyl-butyl acid amides, N-methyl tertbutyl acid amides, N-te t-butylisopropylamide, dibutyl acid amides, di-secondary butyl amide, diisobutyl acid amides, tert-pentyl tert-butylamides, diamyl acid amides, N-methyl hexyl acid amides, dihexyl acid amides, tert-pentyl uncle octyl group acid amides, dioctyl acid amides, two (2-ethylhexyl) acid amides, didecyl acid amides, N-methyl octadecyl acid amides, N-methylcyclohexyl acid amides, N-ethyl cyclohexyl amide, N-isopropylcyclohexyl-acid amides, N-tert-butylcyclohexyl acid amides, dicyclohexyl acid amides, tetramethyleneimine, piperidines, hexamethylene imine, decahydroquinoline, diphenylamine, N-methyl anilide or N-ethyl anilide.

L ^1CAnd L ^2CBe nitrogen or phosphorus independently of one another, preferred nitrogen, and when v is 0 can with the band R ^4COr R ^5CCarbon atom form two keys.When v is 0, L ^1CAnd/or L ^2CWith band R ^4COr R ^5CCarbon atom be preferably formed imino--CR together ^4C=N-or-CR ^5C=N-.When v is 1, L ^1CAnd/or L ^2CWith band R ^4COr R ^5CCarbon atom be preferably formed carboxamido-group-CR together ^4CR ^6C-N ^--or-CR ^5CR ^7C-N ^--.

For example, can confirm X ligand through the metal initial compounds of selecting to be used for synthetic late transition metal complex accordingly ^C, but can also change subsequently.Preferred ligands X ^CBe halogen, for example fluorine, chlorine, bromine or iodine, preferably chlorine.Alkyl, for example methyl, ethyl, propyl group, butyl, vinyl, allyl group, phenyl or benzyl also can be used as X ligand ^COnly also non exhaustive with the mode of example, further X ligand ^CBe trifluoroacetic acid root, BF ₄ ^-, PF ₆ ^-With weak coordination or non-coordination anion (referring to, S.Strauss in Chem.Rev.1993 for example, 93,927-942), B (C for example ₆F ₅) ₄ ^-Acid amides, alkoxide, sulphonate, carboxylate salt and beta-diketon thing also are particularly suitable X ligand ^CIt especially preferably use these to replace some parts in the X ligand, because can derive from raw material cheap and that be easy to obtain.Therefore, work as X ^CDuring for dimethylformamide, methoxyl group, oxyethyl group, isopropoxy, phenoxy, naphthyloxy, trifluoromethanesulfonic acid root, tosic acid root, acetate moiety or Acetyl Acetone thing, obtained especially preferred embodiment.

Change radicals R ^18CPhysical properties can for example be regulated well, like solubleness.Possible organic substituent R ^18CBe for example following groups: C ₁-C ₂₀-alkyl, what it can be for straight or branched, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl; 5-to 7-unit naphthenic base, it can further have C ₆-C ₁₀-aryl is as substituting group, for example Trimetylene, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane or cyclododecane; C ₂-C ₂₀-thiazolinyl; It can for straight chain, ring-type or side chain and two keys wherein can be in inside or end, for example vinyl, 1-allyl group, 2-allyl group, 3-allyl group, crotonyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base; C ₆-C ₂₀-aryl, its can further comprise alkyl and/or contain N or the group of O as substituting group, for example phenyl, naphthyl, xenyl, anthryl, neighbour-,-, right-aminomethyl phenyl, 2,3-, 2; 4-, 2,5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2; 3,5-, 2,3,6-, 2,4; 5-, 2,4,6-or 3,4,5-trimethylphenyl, 2-p-methoxy-phenyl, 2-N, N-dimethylaminophenyl; Perhaps arylalkyl, it can further comprise alkyl as substituting group, for example benzyl, neighbour-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two radicals R ^18CChoose wantonly and can also be connected to form 5-or 6-unit ring, organic group R ^18CCan also be by halogen, for example fluorine, chlorine or bromine replace.At organosilicon substituting group SiR ^19C ₃In, possible radicals R ^19CBe directed against R with the front ^18CMentioned group is identical, wherein two radicals R ^19CChoose wantonly and can also be connected to form 5-or 6-unit ring, for example trimethyl silyl, triethylsilyl, butyl dimetylsilyl, tributyl silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.The preferred C that uses ₁-C ₁₀-alkyl, for example methyl, ethyl, n-propyl, normal-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and vinyl, allyl group, benzyl and phenyl are as radicals R ^18C

X ligand ^CQuantity s depend on the oxidation state of rear transition metal.Therefore quantity s can not provide with the mode of general term.The oxidation state of late transition metal complex in the catalytic activity complex compound is normally known concerning affiliated field those of skill in the art.But, can also use the oxidation state complex compound not corresponding with the oxidation state of active catalyst.Can suitably reduce or this complex compound of oxidation by suitable acvator at that rate.Preferred oxidation state be+3 or+2 iron complex.

D is no lotus donor; Preferred no lotus Lewis base or Lewis acid; For example amine, alcohol, ether, ketone, aldehyde, ester, sulfide or phosphine, it can be bonded in the rear transition metal in the heart or can also be comprised in wherein as the residual solvent of preparation late transition metal complex.

The quantity t of part D can be 0-4, and it depends on the solvent for preparing late transition metal complex and the time of drying of gained complex compound usually, and therefore, it can also be non-integer, for example 0.5 or 1.5.T is preferably 0,1-2.

Embodiment preferred is the iron complex of formula (IIa):

Wherein:

R ^1C-R ^3CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Have the alkylaryl, halogen, the NR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^18C ₂, OR ^18C, SiR ^19C ₃, organic group R wherein ^1C-R ^3CCan also be replaced by halogen, and/or two adjacent group R ^1C-R ^3CCan also be connected to form 5-, 6-or 7-unit ring, and/or two adjacent group R ^1C-R ^3CCan be connected to form and comprise at least one 5-that is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle,

R ^4C-R ^5CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Have the alkylaryl, the NR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^18C ₂, SiR ^19C ₃, organic group R wherein ^4C-R ^5CCan also be replaced by halogen,

R ^8C-R ^11CBe C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Have the alkylaryl, the halogen that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl, i.e. F, Cl, B, I,

R ^12C-R ^17CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Have the alkylaryl, halogen, the NR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^18C ₂, OR ^18C, SiR ^19C ₃, organic group R wherein ^12C-R ^17CCan also be replaced by halogen, and/or two adjacent group R ^12C-R ^17CCan also be connected to form 5-, 6-or 7-unit ring, and/or two adjacent group R ^8C-R ^17CCan be connected to form and comprise at least one 5-that is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle,

Radicals X ^CBe fluorine, chlorine, bromine, iodine, hydrogen, C independently of one another ₁-C ₁₀-alkyl, C ₂-C ₁₀-thiazolinyl, C ₆-C ₂₀Have the alkylaryl, the NR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^18C ₂, OR ^18C, SR ^18C, SO ₃R ^18C, OC (O) R ^18C, CN, SCN, beta-diketon thing, CO, BF ₄ ^-, PF ₆ ^-Or the non-coordination anion of big volume, and radicals X ^COptional can being connected to each other,

Radicals R ^18CBe hydrogen, C independently of one another ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₆-C ₂₀Have the alkylaryl, the SiR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^19C ₃, organic group R wherein ^18CCan also contain halogen or nitrogen-containing group and oxy radical as substituting group, two radicals R ^18CCan also be connected to form 5-or 6-unit ring,

Radicals R ^19CBe hydrogen, C independently of one another ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₆-C ₂₀Has the alkylaryl that has 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl, wherein organic group R ^19CCan also contain halogen or nitrogen-containing group and oxy radical as substituting group, two radicals R ^19CCan also be connected to form 5-or 6-unit ring,

S is 1,2,3 or 4, preferred 2 or 3,

D for no lotus donor and

T is 0-4, preferred 0,1 or 2.

Above-mentioned embodiment and preferred embodiment are equally applicable to E ^2C-E ^4C, R ^1C-R ^3C, X ^C, R ^18CAnd R ^19C

Substituent R ^4C-R ^5CCan in wide region, change.Possible organic substituent R ^4C-R ^5CBe for example following groups: hydrogen, C ₁-C ₂₂-alkyl, what it can be for straight or branched, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl; 5-to 7-unit naphthenic base, it can further have C ₁-C ₁₀-alkyl and/or C ₆-C ₁₀-aryl is as substituting group, for example Trimetylene, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane or cyclododecane; C ₂-C ₂₂-thiazolinyl; It can for straight chain, ring-type or side chain and two keys wherein can be in inside or end, for example vinyl, 1-allyl group, 2-allyl group, 3-allyl group, crotonyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base; C ₆-C ₂₂-aryl, it can further have alkyl as substituting group, for example phenyl, naphthyl, xenyl, anthryl, neighbour-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2; 5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3; 6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl; Or arylalkyl, it can further have alkyl as substituting group, for example benzyl, neighbour-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein organic group R ^4C-R ^5CCan also choose wantonly by halogen, for example fluorine, chlorine or bromine replace.In addition, R ^4C-R ^5CCan be amino N R ^18C ₂Or N (SiR ^19C ₃) ₂, for example dimethylamino, N-pyrrolidyl or pieolinyl.At organosilicon substituting group SiR ^19C ₃In, possible radicals R ^19CWith before to R ^1C-R ^3CMentioned organic group is identical, wherein two radicals R ^19CCan also choose wantonly and be connected to form 5-or 6-unit ring, for example trimethyl silyl, triethylsilyl, butyl dimetylsilyl, tributyl silyl, tri-tert silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR ^19C ₃Group can also be bonded on the carbon that is loaded with it through nitrogen.

Preferred radicals R ^4C-R ^5CBe hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or benzyl, preferable methyl.

Substituent R ^12C-R ^17CCan in wide region, change.Possible organic substituent R ^12C-R ^17CBe for example following groups: C ₁-C ₂₂-alkyl, what it can be for straight or branched, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl; 5-to 7-unit naphthenic base, it can further have C ₁-C ₁₀-alkyl and/or C ₆-C ₁₀-aryl is as substituting group, for example Trimetylene, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane or cyclododecane; C ₂-C ₂₂-thiazolinyl; It can be for straight chain, ring-type or side chain; And two keys wherein can be in inside or end, for example vinyl, 1-allyl group, 2-allyl group, 3-allyl group, crotonyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base; C ₆-C ₂₂-aryl, it can further have alkyl as substituting group, for example phenyl, naphthyl, xenyl, anthryl, neighbour-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2; 5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3; 6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl; Or arylalkyl, it can further have alkyl as substituting group, for example benzyl, neighbour-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two radicals R ^12C-R ^17CCan also choose wantonly and be connected to form 5-, 6-or 7-unit ring, and/or two adjacent group R ^12C-R ^17CCan be connected to form and comprise the 5-that at least one is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle, and/or organic group R ^12C-R ^17CCan also be by halogen, for example fluorine, chlorine or bromine replace.In addition, R ^12C-R ^17CCan be halogen, for example fluorine, chlorine, bromine, amino N R ^18C ₂Or N (SiR ^19C ₃) ₂, alkoxyl group or aryloxy OR ^18C, for example dimethylamino, N-pyrrolidyl, pieolinyl, methoxyl group, oxyethyl group or isopropoxy.At organosilicon substituting group SiR ^19C ₃In, possible radicals R ^19CWith before to R ^1C-R ^3CMentioned carbon organic group is identical, wherein two radicals R ^19CChoose wantonly and can also be connected to form 5-or 6-unit ring, for example trimethyl silyl, triethylsilyl, butyl dimetylsilyl, tributyl silyl, tri-tert silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR ^19C ₃Group can also carry out bonding through oxygen or nitrogen, for example trimethylsiloxy, silicoheptane alcoxyl base, butyl dimethylsilane oxygen base, tributyl siloxy-or tri-tert siloxy-.

Preferred radicals R ^12C, R ^14C, R ^15C, R ^17CBe hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine and bromine, preferred hydrogen.Radicals R ^12C, R ^14C, R ^15CAnd R ^17CBe preferably hydrogen.

Preferred radicals R ^13CAnd R ^16CBe hydrogen, methyl and chlorine.

Preferred radicals R ^8CAnd R ^10CBe hydrogen, especially chlorine.

Preferred radicals R ^9CAnd R ^11CBe methyl.

Preferred R ^12C, R ^14C, R ^15CAnd R ^17CIdentical and R ^13CAnd R ^16CIdentical.This situation is equally applicable to above-mentioned preferred embodiment.

The preparation of compound (A) is described in, J.Am.Chem.Soc.120 for example, ff. (1998) p.4049, J.Chem.Soc., Chem.Commun.1998,849 with WO 98/27124 in.Preferred complex compound (A) is 2, and 6-diacetyl pyridine two (2,6-3,5-dimethylphenyl imines) closes ferrous chloride, 2; 6-diacetyl pyridine two (2,4,6-trimethylphenyl imines) closes ferrous chloride, 2; 6-diacetyl pyridine two (2-chloro-6-aminomethyl phenyl imines) closes ferrous chloride, 2, and 6-diacetyl pyridine two (2,6-diisopropyl phenyl imines) closes ferrous chloride, 2; 6-diacetyl pyridine two (2,6-dichlorophenyl imines) closes ferrous chloride, 2,6-pyridine dicarbaldehyde two (2; 6-diisopropyl phenyl imines) closes ferrous chloride, diacetyl pyridine two (2; 6-dichlorophenyl imines) closes that ferrous chloride, diacetyl pyridine two (2,6-difluorophenyl imines) close ferrous chloride, diacetyl pyridine two (2,6-dibromo phenyl imines) closes ferrous chloride or dibromide separately or tribromide.

Another kind of suitable late transition metal catalyst (A) is the complex compound of formula (IIb):

Wherein:

R ^1A-R ^2ABe hydrogen, C independently of one another ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₆-C ₂₀Have the arylalkyl that has 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl, or SiR ^19C ₃, organic group R wherein ^1A-R ^2ACan also be replaced by halogen, and/or two radicals R ^1A-R ^2ABonding forms 5-or 6-unit ring each other,

Other variable has the implication of being put down in writing in the top formula (IIa).

Another kind of suitable late transition metal catalyst (A) is the complex compound of formula (IIc):

Wherein:

R ^3A-R ^4ABe hydrogen, C independently of one another ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₆-C ₂₀Has the arylalkyl that has 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl, perhaps SiR ^19C ₃, organic group R wherein ^3A-R ^4ACan also be replaced by halogen, and/or under various situation two radicals R ^3A-R ^4ABonding forms 5-or 6-unit ring each other,

G ^ABe the positively charged ion of simple positively charged,

D ^1A, D ^2ABe neutral donor,

W is 0-4,

X is 0,1 or 2,

Z is 0 ,-1 or-2,

Other variable have top formula (IIa) and (IIb) in the implication put down in writing.

Can use promotor, preferably one or more aikyiaiurnirsoxan beta activation late transition metal catalyst (A) suitably.As aikyiaiurnirsoxan beta, can use the compound of describing among the WO 00/31090 for example.Especially suitable aikyiaiurnirsoxan beta is general formula (IV) or open chain (V) or ring-type aluminium alkoxide compound

R wherein ^1D-R ^4DBe C independently of one another ₁-C ₆-alkyl, preferable methyl, ethyl, butyl or isobutyl-and

L is the integer of 1-40, preferred 4-25.

Especially suitable aluminium alkoxide compound is a MAO.

These oligomeric aluminium alkoxide compounds are usually through trialkylaluminium, and the controlled reaction between preferred trimethylaluminium and the water prepares.Usually, the oligomeric aluminium alkoxide compound that obtains in this way exists as the straight chain and the loop chain mixture of all lengths, so l is regarded as mean number.Said aluminium alkoxide compound can also with other metal alkylide, normally aluminum alkyls mix to exist.

In addition, can also use some alkyl wherein to be replaced general formula (IV) or aluminium alkoxide compound (V) by the modified alumoxane of Wasserstoffatoms or alkoxyl group, aryloxy, siloxy-or carboxamido-group replacement.

The suitable promotor that is used for other type of late transition metal catalyst (A) is a hydroxyai upsilonminoxanes.These materials can be for example through at low temperature, and usually being lower than under 0 ℃, to alkylaluminium cpd, based on adding the normal water of 0.5-1.2 whenever measuring aluminium, the preferred normal water of 0.8-1.2 prepares in the especially preferred triisobutyl aluminium.This compound and the purposes in olefinic polymerization thereof for example are being described among the WO 00/24787.The atomic ratio of the rear transition metal of aluminium in the hydroxyai upsilonminoxanes compound and catalyzer (A) is generally 1: 1-100: 1, preferred 10: 1-50: 1, especially preferred 20: 1-40: 1.

Z-type catalyst (B) is affiliated known, in for example ZIEGLERCATALYSTS 363-386 (eds., Springer-Verlag 1995 for G.Fink, R.M ü lhaupt and H.H.Brintzinger), is described.For the application's purpose, the term Z-type catalyst also is included in the catalyzer that is called Ziegler-Natta catalyst in the document.

But Z-type catalyst (B) preferably comprises solid ingredient and the optional preferred particulate inorganic oxide of a kind of titaniferous or vanadium compound, magnesium compound as carrier.

As titanium compound, use trivalent or titanic halogenide or alkoxide usually, the mixture of titan-alkoxide halogen compounds or various titanium compounds is also passable.The example of suitable titanium compound is TiBr ₃, TiBr ₄, TiCl ₃, TiCl ₄, Ti (OCH ₃) Cl ₃, Ti (OC ₂H ₅) Cl ₃, Ti (O-i-C ₃H ₇) Cl ₃, Ti (O-n-C ₄H ₉) Cl ₃, Ti (OC ₂H ₅) Br ₃, Ti (O-n-C ₄H ₉) Br ₃, Ti (OCH ₃) ₂Cl ₂, Ti (OC ₂H ₅) ₂Cl ₂, Ti (O-n-C ₄H ₉) ₂Cl ₂, Ti (OC ₂H ₅) ₂Br ₂, Ti (OCH ₃) ₃Cl, Ti (OC ₂H ₅) ₃Cl, Ti (O-n-C ₄H ₉) ₃Cl, Ti (OC ₂H ₅) ₃Br, Ti (OCH ₃) ₄, Ti (OC ₂H ₅) ₄Or Ti (O-n-C ₄H ₉) ₄The chloride titanium compound of preferred use as halogen.The titanium halide that except titanium, only comprises halogen equally also is preferred, wherein particularly titanium chloride, especially titanium tetrachloride.In vanadium compound, what mention especially can be halogenation vanadium, oxyhalogenation vanadium, alkoxide vanadium and Acetyl Acetone vanadium.Preferred oxidation state is the vanadium compound of 3-5.

In the preparation of solid ingredient, at least a magnesium compound of preferred extra use.Suitable the type compound is halogen-containing magnesium compound, and for example magnesium halide, especially magnesium chloride or magnesium bromide and in a usual manner are for example through obtaining the magnesium compound of magnesium halide with the halogenating agent reaction.Halogen for this purpose is the mixture of chlorine, bromine, iodine or fluorine or two or more halogens, preferred chlorine or bromine, especially chlorine.

Possible halogen-containing magnesium compound is magnesium chloride or magnesium bromide especially.Can obtain halid magnesium compound by it and for example be alkyl magnesium, aryl magnesium, alkoxyl magnesium compound or aryloxy magnesium compound, or the grignard compound.Suitable halogenating agent is for example halogen, hydrogen halide, SiCl ₄Or CCl ₄, preferred chlorine or hydrogenchloride.

The example of suitable not halogen-containing magnesium compound is a magnesium ethide; Di magnesium; Di-isopropyl magnesium; Di-n-butyl magnesium; The di-secondary dibutyl magnesium; Di-t-butyl magnesium; Diamyl magnesium; The normal-butyl magnesium ethide; Normal-butyl sec.-butyl magnesium; Normal-butyl octyl group magnesium; Diphenyl magnesium; Diethoxy magnesium; Two positive propoxy magnesium; Diisopropoxy magnesium; Two n-butoxy magnesium; Two sec.-butoxy magnesium; Two tert.-butoxy magnesium; Two pentyloxy magnesium; The n-butoxy magnesium ethylate; N-butoxy sec.-butoxy magnesium; N-butoxy octyloxy magnesium and two phenoxy magnesium.Wherein, preferably use normal-butyl magnesium ethide or normal-butyl octyl group magnesium.

The example of grignard compound is methylmagnesium-chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethyl magnesium iodide, n-propyl chlorination magnesium, n-propyl bromination magnesium, normal-butyl chlorination magnesium, normal-butyl bromination magnesium, sec.-butyl chlorination magnesium, sec.-butyl bromination magnesium, tertiary butyl chlorination magnesium, tertiary butyl bromination magnesium, hexyl magnesium chloride, octyl group magnesium chloride, amyl group magnesium chloride, isopentyl chlorination magnesium, phenyl-magnesium-chloride and phenyl-magnesium-bromide.

Magnesium compound as the preparation particulate solid except magnesium dichloride or dibrominated magnesium, preferably uses two (C ₁-C ₁₀-alkyl) magnesium compound.

Especially preferred use is commercially available from the for example Z-type catalyst of Grace.

Activating compounds (C) is to be translated into the catalytic activity or the Lewis acid of activatory compound more with the reaction of late transition metal catalyst (A) and Z-type catalyst (B).

Lewis acid is preferably the strong lewis acid compound of general formula (III)

M ^2DX ^1DX ^2DX ^3D (III)

Wherein

M ^2DBe the element of the periodic table of elements 13 families, preferred B, Al or Ga, more preferably B,

X ^1D, X ^2DAnd X ^3DBe hydrogen, C independently of one another ₁-C ₁₀-alkyl, C ₆-C ₁₅Have the haloalkyl or the halogenated aryl that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, alkylaryl, arylalkyl, the alkyl, perhaps fluorine, chlorine, bromine or iodine, preferably halogenated aryl, more preferably pentafluorophenyl group.

Other example of strong lewis acid has mentioned in WO 00/31090.

Suitable aluminium activating compounds (C) is a trialkylaluminium and by its derived compounds, i.e. wherein alkyl alkoxy or the halogen atom substituted compound of chlorine or bromine for example.Said alkyl can be identical or different.Straight chain and branched-chain alkyl can.

Preferred trialkyl aluminium compound, wherein said alkyl has 1-8 carbon atom, for example trimethylaluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, methyl diethyl aluminum and composition thereof.According to preferred embodiment, said activating compounds (C) is selected from trimethylaluminium (TMA), triethyl aluminum (TEA), triisobutyl aluminium (TIBA) and composition thereof.

Suitable activating compounds (C) also comprises borine and boroxin, for example trialkylborane, triarylborane or trimethylboroxin.Especially preferred is the borine that has at least two perfluorination aryl.Especially preferred is X wherein ^1D, X ^2DAnd X ^3DIdentical formula (III) compound; It for example is triphenylborane, three (4-fluorophenyl) borine, three (3; The 5-difluorophenyl) borine, three (4-methyl fluoride phenyl) borine, three (pentafluorophenyl group) borine, three (tolyl) borine, three (3, the 5-3,5-dimethylphenyl) borine, three (3, the 5-difluorophenyl) borine or three (3; 4, the 5-trifluorophenyl) borine.

Preferred three (pentafluorophenyl group) borine that uses.

Compound (C) can through type (III) aluminium or boron cpd and water, alcohol, amphyl, thiophenol verivate or anils reaction and prepare, wherein the particularly important is halo, particularly the pure and mild phenol of perhalogeno.Especially suitable compound for example is a Pentafluorophenol, 1, two (pentafluorophenyl group) methyl alcohol of 1-and 4-hydroxyl-2,2 ', 3,3 ', 4,4 ', 5,5 ', 6,6 '-nine fluorine biphenyl.The example of the combination of formula (III) compound and

acid primary with the most important thing is trimethylaluminium/Pentafluorophenol, two (pentafluorophenyl group) methyl alcohol of trimethylaluminium/1-, trimethylaluminium/4-hydroxyl-2,2 ', 3; 3 ', 4,4 '; 5,5 ', 6; 6 '-nine fluorine xenyls, triethyl aluminum/Pentafluorophenol, triisobutyl aluminium/Pentafluorophenol and triethyl aluminum/4,4 ' dihydroxyl-2,2 '; 3,3 ', 5; 5 ', 6,6 '-octafluoro xenyl hydrate.

In the aluminium and boron cpd of other suitable formula (III), R ^1DBe OH,, preferably have two substituted boracic acids of perfluor aryl, for example (C just as the same in boric acid for example and two substituted boracic acids ₆F ₅) ₂BOH.

The strong lewis acid that is suitable as activating compounds (C) also comprises the reaction product of boric acid and two equivalent trialkylaluminiums, perhaps trialkylaluminium and two equivalent fluorinated, acid, preferred perfluorinated hydrocarbon compound, the for example reaction product of Pentafluorophenol or two (pentafluorophenyl group) boric acid.

Metal in the activating compounds (C) (preferred Al) is preferably 20,000 with the mol ratio of the rear transition metal (preferred Fe) of catalyzer (A): 1-1: 1, and it is different in described at least two polymerization procedures of multiple-stage method of the present invention.

According to preferred embodiment:

-in first polymerization procedure, the mol ratio of the rear transition metal of metal in the activating compounds (C) and catalyzer (A) is 1,500: 1-1: 1, preferred 1,000: 1-100: 1, even more preferably 900: 1-300: 1;

-in second polymerization procedure, the mol ratio of the rear transition metal of the metal of activating compounds (C) and catalyzer (A) is 20,000: 1-1,500: 1, preferred 10,000: 1-2,000: 1, more preferably 9,000: 1-3,000: 1.

Late transition metal complex (A) and Z-type catalyst (B) and activating compounds (C) all are preferred for preferably having the aromatic hydrocarbons of 6-20 carbon atom in the solvent, especially the mixture of YLENE, toluene, pentane, hexane, heptane or these materials.

Catalyst component (A), (B) and (C) can be separately or combine to be used as the catalyst system of olefinic polymerization with other component.Other optional components can be one or more organic or inorganic carriers (D).

Especially,, advantageously use the complex compound of solid form usually, be about to it and be applicable on the solid carrier (D) for late transition metal complex (A) and Ziegler component (B) are used for gas phase or suspending phase polymerization.In addition, the complex compound of load has high productivity.Therefore, can randomly late transition metal catalyst (A) and/or Z-type catalyst (B) be fixed on the organic or inorganic carrier (D), and it be used in the polymerization with its load form.Can for example avoid in reactor drum taking place deposition and form that can controlling polymers like this.

As solid support material; Preferred silica gel, magnesium chloride, aluminum oxide, mesopore material, aluminosilicate, hydrotalcite and the organic polymer of using; For example Vilaterm, Vestolen PP 7052, PS, tetrafluoroethylene or have the polymkeric substance of polar functional group, the for example multipolymer of ethene and propenoate, propenal or vinyl acetate.

The preferred catalyst compsn that is used for method of the present invention comprises one or more carrier component.Late transition metal catalyst (A) and Z-type catalyst (B) can carry out load, perhaps can be only a kind of in two kinds of components be carried out load.In preferred variant, component (A) and (B) all be load.Two kinds of components (A) can be applied on the different carriers with (B), perhaps can be applied to together on the bonded carrier.Preferably with component (A) and (B) be used for the bonded carrier, guaranteeing each catalytic sites relative approximation spatially, thereby make the various polymerization thing of formation realize good mixing.

In order to prepare catalyst system of the present invention; Preferably through physical adsorption or by chemical reaction; Even the reactive group generation covalent bonding of component and carrier surface, and a kind of and/or acvator (C) in a kind of and component (B) in the component (A) is fixed on the carrier (D).

The binding sequence of carrier component (D), late transition metal complex (A), Z-type catalyst (B) and activating compounds (C) is normally unessential.After the single step of said method, can use suitable inert solvent, for example aliphatics or aromatic hydrocarbons wash various midbodys.

Can be independently of one another, for example continuously or side by side fixedly late transition metal complex (A), Z-type catalyst (B) and activating compounds (C).Therefore, carrier component (D) is at first contacted with activating compounds (C), carrier component (D) is at first contacted with Z-type catalyst (B) and/or late transition metal complex (A).Can also before mixing, carry out preparatory activation to Z-type catalyst (B) with one or more activating compounds (C) with carrier (D).The rear transition metal component can for example be reacted with the transition metal complex that has activating compounds (C) simultaneously, perhaps can carry out activation in advance individually through this mode.Can before or after using preactivated Z-type catalyst (B), use preactivated late transition metal complex (A).In a possible embodiment, can also in the presence of solid support material, prepare late transition metal complex (A) and/or Z-type catalyst (B).Other curing is for carrying out prepolymerization to catalyst system using in advance or be not applied in advance under the situation on the carrier.

Said fixing carried out in inert solvent usually, and said inert solvent can remove by filter or evaporate after fixing.Through after each independent step of this method, can use suitable inert solvent, for example aliphatics or aromatic hydrocarbons wash solids and dry.Can also use the catalyzer of still moist load.

In the preparation of the preferred form of load catalyst system, at least a late transition metal complex (A) is contacted with activating compounds (C), it is mixed with the solid support material (D) of dehydration or passivation.Equally, Z-type catalyst (B) is contacted with at least a activating compounds (C) in appropriate solvent, preferably obtain soluble reaction product, adduct or mixts.The preparation that obtains is mixed with the fixed late transition metal complex, and gains are upright to be re-used after connecing or separate solvent, and said solvent is removed wholly or in part.Preferably the load catalyst system to gained carries out dry to guarantee from the hole of solid support material, to remove fully or remove most of solvent.Supported catalyst preferably obtains as free-pouring powder type.The industrial implementation example of aforesaid method is described in WO 96/00243, WO 98/40419 or WO 00/05277.Further preferred embodiment comprises, at first activating compounds (C) is applied on the carrier component (D), and the compound of load is contacted with Z-type catalyst (B) with late transition metal complex (A).

As carrier component (D), preferably use the carrier of fine dispersion, it can be any organic or inorganic solid.Especially, carrier component (D) can be porous support, for example talcum, sheet silicate, for example polynite or mica, the polymer powder of inorganic oxide or fine dispersion (for example, polyolefine or have the polymkeric substance of polar functional group).

The specific surface area of used solid support material is preferably 10-1000m ²/ g, pore volume are 0.1-5ml/g, and mean particle size is 1-500 μ m.The specific surface area of preferred vector is 50-700m ²/ g, pore volume are 0.4-3.5ml/g, and mean particle size is 5-350 μ m.Especially preferred is that the specific surface area of carrier is 200-550m ²/ g, pore volume are 0.5-3.0ml/g, and mean particle size is 10-150 μ m.

Can heat-treat inorganic carrier, for example, in order to remove the water of absorption.This drying treatment is usually at 50-1000 ℃; Carry out under preferred 100-600 ℃; 100-200 ℃ when down dry preferably (for example at decompression and/or rare gas element; Nitrogen) carry out under the atmosphere, perhaps can calcine inorganic carrier down, in order under suitable situation, to obtain the solid structure of hope and/or the surperficial OH concentration of hope at 200-1000 ℃.Can also use the conventional drying agent, metal alkylide for example, preferred alkyl aluminium, chlorosilane or SiCl ₄, perhaps MAO carries out chemical treatment to carrier.The proper process method for example is being described among the WO 00/31090.

Can also carry out chemical modification to inorganic carrier material.For example, use NH ₄SiF ₆Or other fluorizating agent handles silica gel and can cause the silica gel surface to be fluoridized, and it is surperficial perhaps can to produce the silica gel of corresponding modification with the silane treatment silica gel that comprises nitrogenous, fluorine-containing or sulfur-containing group.Solid support material preferably is not formula MgT ₂* y AlR ^v _j(OR ^w) _3-jAdducts, wherein Mg is a magnesium, T is chlorine, bromine or iodine, Al is an aluminium, R ^wBe straight or branched C ₁-C ₁₀-alkyl, y are 6.00-0.05, and j is 3-0.1, R ^vRepresent identical or different substituting group, and for having the alkyl of 1-20 carbon atom, the for example C of straight or branched, ring-type or acyclic ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₂-C ₂₀-alkynyl, C ₆-C ₂₀-aryl, C ₇-C ₂₀-alkylaryl or C ₇-C ₂₀-arylalkyl, it can comprise silicon or germanium atom.

Can also use organic support material; The polyolefin powder of fine dispersion (for example, Vilaterm, Vestolen PP 7052 or PS) for example, and likewise; Preferably should carry out suitable purifying and drying operation before use, make it not contain adhesivity moisture, solvent residues thing or other impurity.Can also use functionalized polymer support, for example based on the polymer support of PS, Vilaterm, Vestolen PP 7052 or polybutylenes, by its functionalized group, for example ammonium or hydroxyl can be fixed at least a catalyst component.Can also use blend polymer.

The inorganic oxide that is suitable as carrier component (D) can find in the 2nd, 3,4,5,13,14,15 and 16 families of the periodic table of elements.For example comprise the mixed oxide of silicon-dioxide, aluminum oxide and element calcium, aluminium, silicon, magnesium or titanium as the preferred oxides of carrier, and corresponding oxide mixture.Other inorganic oxide that can use separately or be used in combination with above-mentioned preferred oxides carrier is for example MgO, CaO, AlPO ₄, ZrO ₂, TiO ₂, B ₂O ₃Or its mixture.

Further preferred inorganic carrier material is inorganic halides, for example MgCl ₂Or carbonate, for example Na ₂CO ₃, K ₂CO ₃, CaCO ₃, MgCO ₃, vitriol, for example Na ₂SO ₄, Al ₂(SO ₄) ₃, BaSO ₄, nitrate salt, for example KNO ₃, Mg (NO ₃) ₂Or Al (NO ₃) ₃

The preferred solid carrier material (D) that uses silica gel as olefin polymerization catalysis because this material can preparation size and structure be applicable to the particle of olefinic polymerization carrier.Have been found that conduct than small-particle, promptly the dried silica gel of the spray of the spherical agglomerated thing of primary particle is particularly useful for the present invention.Silica gel can carry out drying and/or calcining before use.

Used silica gel uses as the powder of fine dispersion usually, and its median size D50 is 5-200 μ m, preferred 10-150 μ m, and especially preferred 15-100 μ m, more preferably 20-70 μ m, its pore volume is generally 0.1-10cm ³/ g, preferred 0.2-5cm ³/ g, specific surface area is 30-1000m ²/ g, preferred 50-800m ²/ g is preferably 100-600m ²/ g.The consumption of Z-type catalyst (A) is preferably such, and promptly the concentration of transition metal in the catalyst system of processing from Z-type catalyst (A) is every g carrier (D) 1-100 μ mol, preferred 5-80 μ mol, especially preferred 10-60 μ mol.

The consumption of late transition metal catalyst (A) preferably makes, is every g carrier (D) 1-200 μ mol from the concentration of rear transition metal in the catalyst system of processing of late transition metal catalyst (A), preferred 5-100 μ mol, especially preferred 10-70 μ mol.The consumption of Z-type catalyst (B) is preferably, and is every g carrier (D) 1-200 μ mol from the concentration of transition metal in the catalyst system of processing of Z-type catalyst (B), preferred 5-100 μ mol, especially preferred 10-70 μ mol.

For catalyst system, can also at first use terminal olefin, preferred straight chain C ₂-C ₁₀-1-alkene, more preferably ethene or propylene carry out prepolymerization to it, and the pre-polymerized catalyst solid with gained is used for actual polymerization then.Be used for pre-polymerized catalyst solid and polymerization monomeric weight ratio above that and be preferably 1: 0.1-1: 1000, preferred 1: 1-1: 200.In addition, among the preparation process of catalyst system or afterwards, can add small amounts of olefins as additive; Preferred terminal olefin; For example vinyl cyclohexane, vinylbenzene or phenyl dimethyl-vinyl silanes add antistatic or suitable inert compound, for example paraffin or oil as modified component.The mol ratio of additive and late transition metal catalyst (A) and Z-type catalyst (B) is generally 1: 1000-1000: 1, preferred 1: 5-20: 1.

The polymerization procedure of multiple-stage method of the present invention can also use industrial known polymerization method to carry out.

Preferred embodiment according to the inventive method:

-in first polymerization procedure, the polymkeric substance that catalyzer (A) produces account for the polymkeric substance for preparing in this step greater than 20%wt., be preferably greater than 30%; With

-in second polymerization procedure, the polymkeric substance that Z-type catalyst (B) produces account for the polymkeric substance for preparing in this step greater than 20%wt., be preferably greater than 30%.

Another embodiment according to the inventive method:

-in first polymerization procedure, the polymkeric substance that Z-type catalyst (B) produces account for the polymkeric substance for preparing in this step greater than 20%wt., be preferably greater than 30%; With

-in second polymerization procedure, the polymkeric substance that catalyzer (A) produces account for the polymkeric substance for preparing in this step greater than 20%wt., be preferably greater than 30%.

Polymerization temperature is preferably-60-350 ℃, and more preferably 20-300 ℃, even more preferably 25-150 ℃.

Polymerization pressure is preferably the 0.5-4000 crust, and more preferably 1-100 clings to, even more preferably 3-40 clings to.

Polymerization procedure can intermittently or carry out continuously.

Polymerization procedure can be in the popular response device of olefinic polymerization, with loose form, suspension form, gas phase or in supercritical medium, carry out.

Can also use the method for high pressure polymerization, solution method, suspension method, stirring vapor phase process and the gas fluidized bed method that in tubular reactor or autoclave, carry out easily.

Mean residence time is preferably 0.5-5 hour, more preferably 0.5-3 hour.Known like affiliated field, the suitable pressure and temperature value of the polymerization procedure of embodiment of the present invention method depends on polymerization method.

Method for high pressure polymerization especially carries out under the 2000-3500 crust preferably at the 1000-4000 crust, in method for high pressure polymerization, also preferably sets high polymerization temperature.The preferred temperature range that is used for these method for high pressure polymerization is 200-320 ℃, more preferably 220-290 ℃.

Under the situation of low-pressure polymerization method, preferably set the softening temperature low at least several years of temperature than this polymkeric substance.Especially, in these polymerizations, preferably temperature is set at 50-180 ℃, preferred 70-120 ℃.

Under the situation of suspension polymerization, preferably at suspension medium, preferred unreactive hydrocarbons, for example the mixture of Trimethylmethane or hydrocarbon perhaps carries out polymerization in monomer itself.Polymerization temperature is preferably-20-115 ℃, and pressure is preferably the 1-100 crust.The solids content of suspension-s is generally 10-80%wt.

Gas phase polymerisation step is preferably at 30-125 ℃, and preferably under the pressure of 1-50 crust, carries out.

In above-mentioned optional polymerization method, especially preferred is vapour phase polymerization (it preferably carries out in gas-phase fluidized-bed reactor), solution polymerization and suspension polymerization (it preferably carries out in annular-pipe reactor and stirred tank reactor).Vapour phase polymerization can also be carried out with condensation or the supercool mode of coagulating, wherein the part recycle gas be cooled to be lower than dew point and as two-phase mixture recycling return reactor drum.

According to further optional embodiment, can use the multi-region reactor drum that comprises two various polymerization connected to one another districts, make polymkeric substance alternately pass through these two districts with preset time.These two districts preferably have different polymerizing conditions, the concentration of different activated compound (C) especially, thus implement two different polymerization stages.This reactor drum for example is being described among the WO 97/04015.If hope, can also polymerization stage be together in series, to form the polymerization polyphone level that two reactors in series connect.In addition, can also be with the molal weight regulator, hydrogen for example, perhaps conventional additives for example static inhibitor be used in the polymerization.

Method of the present invention can obtain density and be preferably 0.900-0.970g/cm ³, more preferably 0.930-0.970g/cm ³Vilaterm.

Said poly M _wBe preferably 100,000-900,000g/mol, more preferably 150,000-750,000g/mol.

Said poly polymolecularity M _w/ M _n, i.e. weight-average molecular weight M _wWith number-average molecular weight M _nRatio be at least 12, preferably at least 15,20-50 more preferably.

Said Vilaterm can be for multimodal; Be preferably bimodally, and comprise at least the first ethene polymers composition, the said first ethene polymers composition comprises ethene polymers; Preferred homopolymer and have first molecular weight; And comprising at least the second ethene polymers composition, the said second ethene polymers composition comprises ethylene copolymer, and has second molecular weight that is higher than said first molecular weight.

Higher molecular weight component and lower molecular weight components in proportions are preferably 5-95 weight %, and more preferably 10-90 weight % especially is preferably 20-80 weight %, and above-mentioned various situation are all based on the higher and summation lower molecular weight composition.

An advantage of the inventive method is exactly; It can obtain to have the multimodal polyethylene of opposite comonomer distribution; Wherein the relatively low said first ethene polymers composition of molecular weight has (if any) comonomer on a small quantity, and the higher relatively said second ethene polymers composition of molecular weight comprises higher co-monomer content.These multimodal polyethylenes demonstrate favourable mechanical property balance.

" opposite comonomer distribution " refers to that comonomer is main or only is combined in the comonomer distribution in the ethene polymers composition of higher molecular weight.

According to preferred embodiment, the multimodal polyethylene that the inventive method obtains comprises:

-Alathon or ethene and up to 2%mol. at least, preferably up to the multipolymer of the more high alpha-olefin of 0.8%mol., its density is 0.950-0.975g/cm ³, preferred 0.960-0.970g/cm ³, M _wBe 10,000-100,000g/mol, preferred 30,000-70,000g/mol, M _w/ M _nBe included between the 3-15, preferably between 4-12 and

-Alathon or ethene and up to 15%mol at least, the multipolymer of the more high alpha-olefin of preferred 0.-10%mol., its density is 0.870-0.955g/cm ³, preferred 0.920-0.965g/cm ³, M _wBe 100,000-2,000,000g/mol, preferred 200,000-800,000g/mol, M _w/ M _nBe included between the 8-80 preferred 10-50.

Preferably more high alpha-olefin has 3-12 carbon atom, more preferably straight or branched C ₂-C ₁₂-1-alkene, especially straight chain C ₂-C ₁₀-1-alkene, for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene or side chain C ₂-C ₁₀-1-alkene, for example 4-methyl-1-pentene.

Said ethylene copolymer preferably comprises at least a more high alpha-olefin, and said more high alpha-olefin has 4-8 carbon atom, more preferably is selected from 1-butylene, 1-hexene and 1-octene.

According to the preferred embodiments of the invention, the multimodal polyethylene that is prepared by method of the present invention has at least 1.5 CH ₃Group/1000 carbon atom, more preferably 1.5-15 CH ₃Group/1000 carbon atom.According to James.C.Randall, JMS-REV.Macromol.Chem.Phys., C29 (2&3), the description among the 201-317 (1989), through ¹³The C-NMR mode is confirmed CH ₃Group/1000 carbon atom, it refers to CH in per 1000 carbon atoms ₃The group total content.

Preferably, said multimodal polyethylene has at least 0.3 vinyl/1000 carbon atom, more preferably 0.5-3 vinyl/1000 carbon atom.Contents of ethylene in per 1000 carbon atoms refers to-CH=CH ₂The content of group, it is through IR, and ASTM D 6248-98 mode is confirmed.

Preferably, said multimodal polyethylene has at least 0.1 vinylidene/1000 carbon atom, more preferably 0.1-0.5 vinylidene/1000 carbon atom.Vinylidene content in per 1000 carbon atoms is through IR, and ASTM D 6248-98 mode is confirmed.

Vinyl inserts normally that polymkeric substance generation termination reaction produces after the ethene, and inferior ethene end group is normally after inserting comonomer, after the polymkeric substance generation termination reaction and form.

The multimodal polyethylene that is obtained by method of the present invention can be advantageously used in preparation fiber, film, moulded work and pipe.

Vilaterm by method preparation of the present invention especially is fit to preparation blown film and casting films, because it has good mechanical character, high impact and high shear strength, and extraordinary optical property, especially transparency and glossiness.

Because it has good mechanical character, therefore said Vilaterm is fit to preparation fiber and moulded work equally, in particular for the material of pipe.

Following analytical procedure is used for the character of confirming that this specification sheets and embodiment report.

Gpc analysis

Use the method for describing among the DIN 55672-1:1995-02 (February nineteen ninety-five), average Mn, Mw and Mw/Mn through the high-temperature gel permeation chromatography method is confirmed molar mass distribution and especially derived and have following deviation: solvent 1; 2,4-trichlorobenzene (TCB), 135 ℃ of device and solution temperatures; PolymerChar (Valencia; Paterna 46980, and Spain) the IR-4 infrared detector is as concentration detector, and it can use with TCB.

Use WATERS Alliance 2000, it has been equipped with the following pre-column SHODEX UT-G that is connected in series and separator column SHODEX UT 806M (3x) and SHODEX UT 807.The vacuum distilling solvent also carries out stabilization with the 2,6 di tert butyl 4 methyl phenol of 0.025 weight % under N2.Used flow velocity is 1ml/min, injects 500 μ l, and polymer concentration is 0.01%-0.05%w/w.Use Polymer Laboratories (to be Varian now; Inc.; Essex Road, Church Stretton, Shropshire; SY66AX, monodisperse polystyrene UK) (PS) (at 580g/mol to the scope up to 11600000g/mol) standard and other n-Hexadecane are set up the molecular weight calibration.Adopt then universal calibration method (Benoit H., Rempp P.and Grubisic Z., & in J.Polymer Sci., Phys.Ed., 5, 753 (1967)) and make calibration curve be suitable for Vilaterm (PE).Mark-Houwing parameter used for PS is: k _Ps=0.000121dl/g, α _Ps=0.706, k for PE _Pe=0.000406dl/g, α _Ps=0.725, effective in 135 ℃ TCB.Use NTGPC_ contrast _ V6.02.03 and NTGPC_V6.4.24 (hs GmbH, Hauptstra β e 36, D-55437 Ober-Hilbersheim) to carry out data logging, correction and calculating respectively.

IR analyzes

According to ASTM D 6248-98, confirm density [g/cm with IR ³].

According to ASTM D 6248-98, adopt IR to confirm vinyl double bond content, i.e. contents of ethylene/1000 carbon atom.

Adopt IR, ASTM D 6248-98 confirms trans double bond content, promptly trans linkage content/1000 carbon atoms.

According to ASTM D 6248-98, adopt IR to confirm the content of comonomer.

According to DIN EN ISO 11885, measure the amount of aluminium, iron, magnesium and titanium in the catalyzer with the ICP-OES method.

The following example has been explained the present invention, but does not limit invention scope.

Embodiment 1

2, the preparation that 6-diacetyl pyridine two (2-chloro-6-aminomethyl phenyl anils) closes ferrous chloride

2,6-diacetyl pyridine two (2-chloro-4,6-dimethyl-anilss) synthetic

To 2, the 6-diacetyl pyridine (35g adds 2-chloro-4 in THF 0.21mol) (1.21) solution, and the 6-xylidine (76.7g, 2.3eq) and Sicapent (45g).Reaction mixture refluxed is spent the night.Add 2-chloro-4 afterwards again, (25g 0.7eq) and Sicapent (25g), and refluxes and spends the night the 6-xylidine once more.Suspension-s is cooled to 22 ℃, filters and with THF (75ml) washed twice.Mother liquor is concentrated (90%) and adds methyl alcohol with precipitated product, with twice of methyl alcohol (50ml) washed product and dry under high vacuum.Isolate 68.8g yellow powder (y=73.1%).

2, two (2-chloro-4, the 6-dimethyl-anils) FeCl of 6-diacetyl pyridine ₂Synthetic

To 2, (150g adds a FeCl by part in THF 0.34mol) (31) solution to 6-diacetyl pyridine two (2-chloro-4,6-dimethyl-anils) under 22 ℃ ₂.4H ₂O (64.6g, 0.95eq).Reaction mixture becomes blueness.After stirring 3 hours under 22 ℃, filter blue suspension-s, wash 3 times and drying under high vacuum with THF (300ml).Isolate 174.0g blue powder (y=90%).

Embodiment 2

The preparation of Z-type catalyst

Description according to embodiment among the WO2004/106388 14 prepares catalyzer, and said catalyzer comprises and loads on MgCl ₂(EtOH) TiCl on the adducts ₄With AcOEt as electron donor(ED).

Embodiment 3

The preparation of hybrid catalyst system

In the two neck circular glass stills of the 250ml that has been equipped with vacuum Teflon whisking appliance, under argon atmospher, be suspended in the 15.3g Z-type catalyst of preparation among the embodiment 2 in the 40ml heptane and be cooled to 0 ℃.

297mg iron catalyst with preparation among the embodiment 1 joins in the 30%wt toluene solution of 15.5ml MAO individually, and at room temperature stirs 1 hour.The catalytic solution of gained is cooled to 0 ℃ and under agitation in 60 minutes, join in the Z-type catalyst suspension-s, and temperature remains on 0 ℃ ± 2 ℃.Drip when finishing, suspension-s was at room temperature kept 1 hour.The color of filter cake is become brown by reddish brown, become black at last.Filter solvent under the vacuum, at room temperature filter cake is suspended in the 30ml heptane afterwards, stirred 15 minutes and filtering solvent once more; This step repeats 2 times.

Under room temperature, vacuum, be free-pouring powder at last, in order to reach the residue volatile matter of 5-10%wt with the catalyzer drying.

Collect the 18.27g dry catalyst and, obtain following result with the analysis of ICP method:

Al＝9.0％wt

Mg＝11.4％wt

Ti＝2.0％wt

Fe＝0.16％wt

The mol ratio of the Fe of the Ti of Z-type catalyst (B) and iron catalyst (A) is 14.

Embodiment 4

Vinyl polymerization

Under the vacuum polyethylene powders of 80g granularity greater than 1mm (the screening composition is 80 ℃ of dry 24 hours and storages under argon gas down) is loaded in the 1L stainless steel autoclave, under vacuum, is heated to afterwards up to 70 ° of maintenances 30 minutes.

With argon gas reactor drum is forced into 1 crust-a; 1ml

AS 100-solution (0.55ml is provided

AS 100 from Costenoble, and fill heptane obtain to 100ml) is fed in the reactor drum and stirred 10 minutes.

The toluene solution (0.771mol/L TIBA) of 1ml TIBA is fed in the reactor drum and stirred 10 minutes.

Inject the hybrid catalyst system of 56mg embodiment 3 preparations, it is free-pouring powder.Reactor drum is heated to 70 ℃ also with 10 crust argon gas and 0.5 crust pressurized with hydrogen, until the total pressure that reaches 10.5 crust-g.The mol ratio of the Al of TIBA and the iron of hybrid catalyst system is 480.

With ethylene feed to reactor drum until the pressure that reaches 20.5 crust-g; Continuous feeding ethylene 60 minutes, reactor pressure is remained on after the 20.5 crust-g, emit monomer to 0.5 crust-g suddenly to stop polymerization.

Under the situation of not emitting polymkeric substance, the toluene solution (0.771mol/LTIBA) of 10mL TIBA is fed to reactor drum and stirred 10 minutes; The mol ratio of the Al of TIBA and the iron of hybrid catalyst system is 4800.

With 10.5 crust-g argon gas, 0.5 crust-g hydrogen and ethene autoclave is pressurizeed once more, reach 20.5 crust-g until stagnation pressure; 60 minutes ethene of charging also remains on reactor pressure after the 20.5 crust-g, stops polymerization, reactor drum decompression and cooling.From reactor drum, take out polymkeric substance, drying under reduced pressure and screening separation from initial charge.Obtain the 125g Vilaterm.

The condition of this method and the character of resulting polymers have been listed in the following table 1 and 2.

Embodiment 5

Vinyl polymerization

Under the vacuum polyethylene powders (screening composition 80 ℃ down dry 24 hour and under argon gas storages) of 80g granularity greater than 1mm is loaded in the 1L stainless steel autoclave, under vacuum, is heated to 70 ° afterwards and kept 30 minutes.

With argon gas reactor drum is forced into 1 crust-a; 1ml

AS 100-solution (0.55ml is provided

Inject the hybrid catalyst system of 33mg embodiment 3 preparations, it is free-pouring powder.Reactor drum is heated to 70 ℃ also with 10 crust argon gas and 0.5 crust pressurized with hydrogen, until the total pressure that reaches 10.5 crust-g.The mol ratio of the Al of TIBA and the iron of hybrid catalyst system is 810.

With ethylene feed to reactor drum until the total pressure that reaches 20.5 crust-g; Continuous feeding ethylene 60 minutes, reactor pressure is remained on after the 20.5 crust-g, emit monomer to 0.5 crust-g suddenly to stop polymerization.

Under the situation of not emitting polymkeric substance, the toluene solution (0.771mol/LTIBA) of 10mL TIBA is fed to reactor drum and stirred 10 minutes; The mol ratio of the Al of TIBA and the iron of hybrid catalyst system is 8100.

With 10.5 crust-g argon gas, 0.5 crust-g hydrogen and ethene autoclave is pressurizeed once more, reach 20.5 crust-g until pressure.60 minutes ethene (2L ethene) of charging and with reactor pressure remain on 20.5 crust-g down after, stop polymerization, reactor drum decompression and cooling.From reactor drum, take out polymkeric substance, drying under reduced pressure and screening separation from initial charge.Obtain the 102g Vilaterm.

Embodiment 6

Vinyl polymerization

With argon gas reactor drum is forced into 1 crust-a; 1ml

AS 100-solution (0.55ml is provided

Inject the hybrid catalyst system of 50mg embodiment 3 preparations, it is free-pouring powder.Reactor drum is heated to 70 ℃ also with 10 crust argon gas and 0.5 crust pressurized with hydrogen, until the total pressure that reaches 10.5 crust-g.The mol ratio of the Al of TIBA and the iron of hybrid catalyst system is 540.

Under the situation of not emitting polymkeric substance, the toluene solution (0.771mol/LTIBA) of 10mL TIBA is fed to reactor drum and stirred 10 minutes; The mol ratio of the Al of TIBA and the iron of hybrid catalyst system is 5400.

With 10.5 crust-g argon gas, 0.5 crust-g hydrogen and 10 crust-g ethene autoclave is pressurizeed once more, reach 20.5 crust-g until stagnation pressure; 60 minutes ethene of charging also remains on reactor pressure after the 20.5 crust-g, stops polymerization, reactor drum decompression and cooling.From reactor drum, emit polymkeric substance, drying under reduced pressure and screening separation from initial charge.Obtain the 67g Vilaterm.

Comparative example 1

Vinyl polymerization

With argon gas reactor drum is forced into 1 crust-a; 1ml

AS 100-solution (0.55ml is provided AS 100 from Costenoble, and fill heptane obtain to 100ml) is fed in the reactor drum and stirred 10 minutes.

Inject the hybrid catalyst system of 32mg embodiment 3 preparations, it is free-pouring powder.

Reactor drum is heated to 70 ℃ also with 10 crust argon gas and 0.5 crust pressurized with hydrogen, until the total pressure that reaches 10.5 crust-g.The mol ratio of the Al of TIBA and the iron of hybrid catalyst system is 840.

With ethylene feed to reactor drum until the pressure that reaches 20.5 crust-g (about 5L) and begin polymerization; Charging 10ml 1-hexene in the process of charging ethene.

Continuous feeding ethylene 60 minutes, reactor pressure is remained on after the 20.5 crust-g, emit monomer suddenly to stop polymerization, reactor drum decompression and cooling.From reactor drum, take out polymkeric substance, drying under reduced pressure and screening separation from initial charge.Obtain the 32g Vilaterm.

Comparative example 2

Vinyl polymerization

With argon gas reactor drum is forced into 1 crust-a; 1ml AS 100-solution (0.55ml is provided

Inject the hybrid catalyst system of 28mg embodiment 3 preparations, it is free-pouring powder.Reactor drum is heated to 70 ℃ also with 10 crust argon gas and 0.5 crust pressurized with hydrogen, until the total pressure that reaches 10.5 crust-g.The mol ratio of the Al of TIBA and the iron of hybrid catalyst system is 9600.

Continuous feeding ethylene 60 minutes, reactor pressure is remained on after the 20.5 crust-g, emit monomer suddenly to stop polymerization, reactor drum decompression and cooling.From reactor drum, emit polymkeric substance, drying under reduced pressure and screening separation from initial charge.Obtain the 44g Vilaterm.

Table 1

Embodiment	Catalyzer [mg]	TIBA [ml]	1-hexene [ml]	Polymerization time [min]	Polymerization temperature [℃]	Productive rate [g]	Active [kg/g/h]
								Embodiment 4	56	1+10	0	60+60	70	125	1.1
Embodiment 5	33	1+10	0	60+60	70	102	1.5
								Embodiment 6	50	1+10	0	60+60	70	67	0.7
Comparative example 1	32	1	10	60	70	32	1.0
								Comparative example 2	28	10	10	60	70	44	1.6

Table 2

Embodiment	M _w·10 ^-3 [g/mol]	?M _w/M _n	Density [g/cm ³]	Total CH ₃ [1/1000C]	Trans double bond [1/1000C]	Vinyl double bond [1/1000C]	Hexene [%wt]
								Embodiment 4	238.3	20	0.960	＜0.01	0.81	0.14	--
Embodiment 5	271.3	25	0.961	＜0.01	0.91	0.20	--
								Embodiment 6	138.1	19	0.964	＜0.01	1.22	0.18	--
Comparative example 1	60.7	12	0.966	0.01	1.90	0.21	＜0.8
								Comparative example 2	275.7	26	0.943	＜0.01	0.29	0.23	1.2

Comparative example 1 and 2 shows, can optionally control the activity of various polymerization catalysts used in the inventive method through the amount that changes activating compounds.Therefore, shown in embodiment 4-6,, can control the molecular weight of gained Vilaterm composition and the composition of comonomer through changing this amount.

Claims

1. multi-stage process that is used for alkene homopolymerization or copolymerization, it is included in catalyst system and exists down, at least two polymerization procedures, makes ethene and randomly one or more more high alpha-olefin polymerizations, and wherein said catalyst system comprises:

-at least a polymerizing catalyst (A) based on the rear transition metal component, it has and brings to few two ortho positions, the tridentate ligand of ortho position-disubstituted aryl,

-at least a Ziegler polymerization catalyst (B) and

-at least a lewis acid activation compound (C),

Wherein in described at least two polymerization procedures, the metal of said activating compounds (C) is different with the mol ratio of the rear transition metal of said catalyzer (A),

Said multi-stage process comprises:

-the first polymerization procedure, wherein the mol ratio of the rear transition metal of metal in the activating compounds (C) and catalyzer (A) is 1,500: 1-1: 1 and

-the second polymerization procedure, wherein the mol ratio of the rear transition metal of metal in the activating compounds (C) and catalyzer (A) is 10,000: 1-1,500: 1.

2. the multi-stage process of claim 1, wherein the mol ratio of the rear transition metal of the transition metal of Z-type catalyst (B) and catalyzer (A) is 500: 1-1: 100.

3. the multi-stage process of claim 2, wherein the mol ratio of the rear transition metal of the transition metal of Z-type catalyst (B) and catalyzer (A) is 100: 1-1: 50.

4. each multi-stage process among the claim 1-3, wherein:

-in first polymerization procedure, the polymkeric substance that catalyzer (A) produces account for the polymkeric substance for preparing in the first step greater than 20%wt.; With

-in second polymerization procedure, the polymkeric substance that Z-type catalyst (B) produces account for the polymkeric substance for preparing in second step greater than 20%wt..

5. each multi-stage process among the claim 1-3, wherein first and second polymerization procedures carry out in the reactor drum of two serial operations.

6. the multi-stage process of claim 1, wherein said catalyst system loads on one or more inorganic oxides.

7. the multi-stage process of claim 1 wherein uses one or more aikyiaiurnirsoxan beta deactivated catalysts (A).

8. the multi-stage process of claim 1, wherein catalyzer (A) has formula (I):

Wherein:

M is Fe or Co,

E ^1CBe nitrogen or phosphorus,

E ^2C-E ^4CBe carbon, nitrogen or phosphorus independently of one another,

R ^1C-R ^3CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Have the alkylaryl, halogen, the NR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^18C ₂, OR ^18C, SiR ^19C ₃, organic group R wherein ^1C-R ^3CCan also be replaced by halogen, and/or two adjacent radicals R ^1C-R ^3CCan also be connected to form 5-, 6-or 7-unit ring, and/or two adjacent radicals R ^1C-R ^3CCan be connected to form and comprise at least one 5-that is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle,

R ^4C-R ^7CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Have the alkylaryl, the NR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^18C ₂, SiR ^19C ₃, organic group R wherein ^4C-R ^7CCan also be replaced by halogen, and/or two geminals or adjacent radicals R ^4C-R ^7CCan be connected to form 5-, 6-or 7-unit ring, and/or two geminals or adjacent group R ^4C-R ^9CCan be connected to form and comprise at least one 5-that is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle, and when v is 0, R ^6CFor being connected to L ^1CKey, and/or R ^7CFor being connected to L ^2CKey, make L ^1CAnd have R ^4CCarbon atom form two keys, and/or L ^2CAnd have R ^5CCarbon atom form two keys,

L ^1C-L ^2CBe nitrogen or phosphorus independently of one another,

R ^8C-R ^11CBe C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Have the alkylaryl that has 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl, or halogen,

R ^12C-R ^17CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Have the alkylaryl, halogen, the NR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^18C ₂, OR ^18C, SiR ^19C ₃, organic group R wherein ^12C-R ^17CCan also be replaced by halogen, and/or two adjacent group R ^8C-R ^17CCan be connected to form 5-, 6-or 7-unit ring, and/or two adjacent group R ^8C-R ^17CBe connected to form and comprise at least one 5-that is selected from the atom of N, P, O and S, 6-or 7-unit heterocycle,

V is 0 or 1 independently,

Radicals X ^CBe fluorine, chlorine, bromine, iodine, hydrogen, C independently of one another ₁-C ₁₀-alkyl, C ₂-C ₁₀-thiazolinyl, C ₆-C ₂₀Have the alkylaryl, the NR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^18C ₂, OR ^18C, SR ^18C, SO ₃R ^18C, OC (O) R ^18C, CN, SCN, beta-diketon thing, CO, BF ₄ ^-, PF ₆ ^-Or the non-coordination anion of big volume, radicals X ^CRandomly can be connected to each other,

Radicals R ^18CBe hydrogen, C independently of one another ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₆-C ₂₀Have the alkylaryl, the SiR that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl ^19C ₃, organic group R wherein ^18CCan also be by halogen or nitrogen-containing group and oxy radical replacement and two radicals R ^18CCan also be connected to form 5-or 6-unit ring,

Radicals R ^19CBe hydrogen, C independently of one another ₁-C ₂₀-alkyl, C ₂-C ₂₀-thiazolinyl, C ₆-C ₂₀Has the alkylaryl that has 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl, wherein organic group R ^19CCan also be by halogen or nitrogen-containing group and oxy radical replacement and two radicals R ^19CCan also be connected to form 5-or 6-unit ring,

S is 1,2,3 or 4,

D for no lotus donor and

T is 0-4.

9. the multi-stage process of claim 8, wherein

R ^8C, R ^10CBe independently of one another halogen and

R ^9C, R ^11CBe C independently of one another ₁-C ₂₂-alkyl, C ₂-C ₂₂-thiazolinyl, C ₆-C ₂₂Has the alkylaryl that has 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, the alkyl.

10. claim 8 or 9 multi-stage process, wherein R ^13CAnd R ^16CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl or halogen.

11. the multi-stage process of claim 8, wherein catalyzer (A) has formula (IIa):

Wherein said variable has the implication described in the claim 8.

12. the multi-stage process of claim 11, wherein R ^13CAnd R ^16CBe hydrogen, C independently of one another ₁-C ₂₂-alkyl or halogen.

13. the multi-stage process of claim 1, wherein said Z-type catalyst (B) comprise titanium or vanadium compound and the magnesium compound that loads on the particulate inorganic oxide.

14. the multi-stage process of claim 1, wherein said activating compounds (C) is the Lewis acid of general formula (III)

M ^2DX ^1DX ^2DX ^3D (III)

Wherein

M ^2DBe the element of the periodic table of elements 13 families,

X ^1D, X ^2DAnd X ^3DBe hydrogen, C independently of one another ₁-C ₁₀-alkyl, C ₆-C ₁₅Have the haloalkyl or the halogenated aryl that have 6-20 carbon atom on 1-10 carbon atom and the aryl on-aryl, alkylaryl, arylalkyl, the alkyl, or fluorine, chlorine, bromine or iodine.

15. the multi-stage process of claim 14, wherein M ^2DBe B, Al or Ga.

16. the multi-stage process of claim 15, wherein said activating compounds (C) is selected from trimethylaluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, methyl diethyl aluminum and composition thereof.

17. the multi-stage process of claim 16, wherein said activating compounds (C) is selected from trimethylaluminium, triethyl aluminum, triisobutyl aluminium and composition thereof.

18. the multi-stage process of claim 1, being used to prepare density is 0.900-0.970g/cm ³, M _wBe 100,000-900,000g/mol and M _w/ M _nVilaterm at least 12.

19. the multi-stage process of claim 1 is used to prepare multimodal polyethylene, said multimodal polyethylene comprises:

-Alathon or ethene and up to the multipolymer of the more high alpha-olefin of 2%mol., its density is 0.950-0.975g/cm at least ³, M _wBe 10,000-100,000g/mol, M _w/ M _nBe included between the 3-15 and

-Alathon or ethene and up to the multipolymer of the more high alpha-olefin of 15%mol, its density is 0.870-0.955g/cm at least ³, M _wBe 100,000-2,000,000g/mol, M _w/ M _nBe included between the 8-80.